Distinct Activity of the Oxyl Fe(III) -O Group in the Methane Dissociation by Activated Iron Hydroxide: DFT Predictions
Full article
| Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Chemical Physics Letters
ISSN: 0009-2614
, E-ISSN: 1873-4448
|
| Output data |
Year: 2015,
Volume: 640,
Pages: 94-100
Pages count
: 7
DOI:
10.1016/j.cplett.2015.10.016
|
| Authors |
Shubin Aleksandr A.
1
,
Ruzankin Sergey Ph.
1
,
Zilberberg Igor L.
1
,
Parmon Valentin N.
1
|
| Affiliations |
| 1 |
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
|
|
Funding (1)
|
1
|
Russian Science Foundation
|
14-13-01155
|
The abstraction of hydrogen from methane on the terminal iron-oxo group in the ferryl FeIVdouble bond; length as m-dashO and oxyl FeIIIsingle bondOradical dot states, the hydrogen peroxide group Fesingle bondOOH and the peroxo group Fesingle bondOOsingle bondFe created in iron hydroxide was modeled by means of the density functional theory. The active groups were built using the Fe4O4(OH)4 starting complex having one hydrogen removed imitating the effect of the external oxidizer. Among considered groups the oxyl group is predicted to have the highest reactivity. A clear distinction in reactivity between the FeIIIsingle bondOradical dot and FeIVdouble bond; length as m-dashO quasi-degenerate states has been attributed to the sign of terminal oxygen spin polarization.